Herbicidal and insecticidal composition



United States Patent C) 6 Claims. 01. 71-90 ABSTRACT OF THE DISCLOSUREThe invention is directed to an insecticidal and herbicidal compositionconsisting essentially of an inert carrier and an effective amount of acompound of the formula:

wherein R R R R R R R and R are each a substituentselected from theclass consisting of hydrogen and lower alkyl; 12 is an integer from to1; and Q is a substituent selected from the group consisting of H X and-PZ(OR in which X is a halogen atom, Z is a substituent selected fromthe group consisting of oxygen and sulfur, and R stands for lower alkyl.

. 'This application is a divisional of my copending application forLetters Patent, Ser. No. 328,204, filed on Dec. 5, 1963, now US. PatentNo. 3,318,910.

- The present invention relates to novel pesticidal compounds. Moreparticularly, the invention relates to S-membered and 6-mernberedheterocyclic sulfur compounds containing in the two-position thereof animino substituent, to methods for the preparation of such compounds, andto the utilization of the heterocyclic sulfur compounds as the activecomponent in a pesticidal composition.

The novel hetero-sulfur compounds prepared in accordance with thepresent invention may be represented by the formula:

wherein each of the Rs is either hydrogen or lower alkyl; n is aninteger from 0 to 1; Q is either a H X or PZ(OR group, in which X is ahalogen atom, such as fluoro, chloro, bromo or iodo; R stands for loweralkyl and Z represents oxygen or sulfur.

In general, the compounds of the invention may be synthesized in astraightforward and simple manner. Either a 4-acylthiobutyronitrile or aS-acylthiovaleronitrile as prepared by reacting a thiolalkanoic acidwith either a 4-halobutyronitrile or a S-halovaleronitrile in analkaline medium, is reacted with a hydrohalide, such as hydrochloricacid, either in an aqueous or alcoholic menstruum. In this manner,either the acylthiobutyronitrile or the acylthiovaleronitrile isconverted to form either a 2-iminothiolane hydrochloride or a2-iminothiane hydrochloride, respectively. The latter is then reactedwith an 0,0-di(lower)- alkylphosphorohalothioate or an O,O-di(l0wer)alkylphosphorohaloate in the presence of an acid acceptor such astriethylamine or sodium acetate, to obtain the desired product in goodyield and purity.

The over-all reaction may be written as follows:

R2 \Rl/n Ra Ra 4-Halobutyronitrile Thiolalkanic acid 5-Halovaleronitri1eCN Rec-SH 2-Iminothio1ane hydrohallde or 2-Iminothiane hydrohalide wheren and all the Rs are as defined in [I] above.

Dlalkoxyphosphinyliminothiolane OI Dialkoxyphosphinyliminothiane where Zis an oxygen or sulfur atom, R is lower alkyl, and all the remaining Rs,X and n are the same as defined in [1] above.

Illustrative of the 4-halobutyronitrile and the 5-halovaleronitrilereactants which can be employed herein are:

4-bromobutyronitrile, S-bromovaleronitrile, 4-chloro-3-methylbutyronitrile, 4-chlorobutyronitrile,

3 4-iodobutyronitrile, 4-bromo-4-methylbutyronitrile,

5 -bromo-5 -methylva1eronitrile, 4-fiuorobutyronitrile,5-bromo-5-ethylvaleronitrile, and 4-bromo-2,3-dimet-hylbutyronitrile.

The aforementioned nitriles can preferably be dissolved in an alcoholicmedium so as to cause more rapid completion of the reaction.

For purposes of reaction in step [I], any thiol(lower) alkanoic acid canbe employed. For instance, ,thiolacetic acid, thiolpropionic acid orthiolbutanoic acid may advantageously be utilized.

In general, the typical phosphorohalothioates or the phosphorohaloatereactants employed herein are: 0,0-dimethyl phosphorochloridothioate,.0,0-diethyl phosphorochloridothioate,

O-methyl, O-ethyl phosphorochloridothioate, 0,0-di-isopropylphosphorobromidothioate, 0,0-di-n-butyl phosphorochloridothioate,0,0-di-sec.-pentyl phosphoroiodothioate, 0,0-dimethylphosphorochloridate, and 0,0-diethyl phosphorochloridate.

To facilitate a further understanding of the invention, the followingexamples are presented primarily for purposes of illustrating certainmore specific details thereof. The examples are not to be taken aslimitative of the invention. Unless otherwise noted, all parts are byweight and the analyses are in percent.

EXAMPLE 1 Preparation of Z-iminothiolane hydrochloride To a suitablereaction vessel containing 74.8 parts of 4-acetylthiobutyronitrile(prepared by reacting approximately one mol of 4-bromobutyronitrile withone mol of thiolacetic acid in the presence of potassium carbonate) in200 parts by volume of methanol are added 275 parts of 2 N hydrogenchloride in methanol. The reaction contents are vigorously stirred forabout eighteen hours. Methanol is next distilled and the reaction vesselis icecooled. 250 parts by volume of ether are then added. Precipitatedsolids are collected, washed with additional ether whereby 40.4 parts ofa colorless product are obtained. The filtrate is then concentrated andthe addition of ether affords a second crop of crystals amounting to 7.3parts. The fractions are further purified by vacuum sublimation at 70 C.to 100 C. at 0.2 mm. Hg. .A total yield of 47.7 parts, equal to 66.3percent, is obtained. Themelting point for 2-iminothiolane hydrochlorideis 190 C. to 195 C. having the following analysis:

Calculated for C H ClNS: C, 34.9; H, 5.9; Cl, 25.8; S, 23.3. Found: C,34.7; H, 5.7; Cl, 25.7; S, 23.2.

Substituting 4-acetylthio-4-methylbutyronitrile for theacetylthiobutyronitrile reactant above, a good yield of 2-imino-S-methylthiolane hydrochloride is obtained in good purity.

EXAMPLE 2 The procedure of Example 1 is followed in every detail, exceptthat S-acetylthiovaleronitrile is employed in lieu of4-acetylthiobutyronitrile. A good yield of Z-iminothiane hydrochlorideis obtained.

EXAMPLE 3 Repeating Example 1 in every detail, except that 5-acetylthio-S-methylvaleronitrile is substituted for the 4-acetylthiobutyronitrile reactant, there is obtained in good yield andpurity, 2-irnino-6-methylthiane hydrochloride.

EXAMPLE 4 Preparation of Z-diethoxyphosphinothioyliminothiolane To 100parts by volume of acetone stirred at between about 20 C. and 25 C. in asuitable reaction vessel are added 10 parts of 2-iminothiolanehydrochloride, 13.7 parts of 0,0-diethy1 phosphorochloridothioate, and12 parts of sodium acetate. The mixture isthen refluxed for about twelvehourswhile withdrawing samples intermittently. Upon infrared examinationof the samples obtained, the reaction is found to be. substantiallycomplete within one hour.

Resultant solids are collected, ether-washed and the filtrate isconcentrated in vacuo. Remaining oily substance is next taken up in anether-benzene mixture and the mixture is washed employing water andpotassium carbonate solution. After drying and concentrating the washedmixture, molecular distillation of the residual oil affords 13.9 partsor 75.5 percent of a colorless product possessing a refractive index (12equal to 1.5467, and having the following analysis:

Calculated for C H NO PS C, 37.9; H, 6.4; P, 12.2; S, 25.3. Found: C,37.8; H, 6.0; P, 12.2; S, 25.3.

Substituting for the diethyl phosphorochloridothioate reactant in theabove example 0,0-diethyl phosphorochloridate, and, for the sodiumacetate, triethylamine, 2- diethoxyphosphinyliminothiolane is obtainedin good yield and purity.

EXAMPLE 5 Preparation 0] Z-dimethoxyphosphinothioyliminothiolaneEmploying the procedure of Example 2 above, a mixture of 10 parts ofZ-iminothiolane hydrochloride, 11.7 parts of 0,0-dimethylphosphorochloridothioate and 12.5 parts of sodium acetate is reacted. 11parts equal to 67.2 percent of a pale yellow product having a refractiveindex (12 equal to 1.5742 is obtained which is identified as2-dimethoxyphosphinothioylirninothiolane, analyzing, in percent asfollows:

Calculated for C H NO PS C, 32.0; H, 5.4; P, 13.8; S, 28.5. Found: C,32.4; H, 5.7; P, 14.4; S, 28.9.

It is an advantage of the present invention that the compoundshereinabove defined can be utilized by incorporating them into a varietyof inert carriers or diluents. For instance, each of the compounds canbe dissolved inan inert organic solvent, such as acetone, ethyl acetate,ethyl alcohol, benzene, xylene, kerosene or equivalents thereof;

or the compounds may be admixed with an inert solid carrier, as forexample, fullers earth, precipitated hydrated silicon dioxide, activatedcarbon, bentonite, attaclay, celite, kaolin clay, a mixture ofbentoniteand attapulgite, and the like. If desired, a suspension of the compoundsmay be prepared by employing a non-solvent therefor. In that event, itis advantageous to add thereto any commercially available dispersing orsurface-active agent of the anionic, cationic or nonionic types, ormixtures of the same. Illustrative surface-active agents are: thealkylaryl sulfonates, the calcium salt of an oil-soluble sulfonate andpolyoxyethylene. ethers, such as Emcol H 140, the sodium salt of apolymerized propyl naphthalene sulfonic acid, formed by condensingformaldehyde with a propyl naphthalene sodium sulfonate, the alkylarylpolyether alcohols, the ethylene oxide addition products of such estersas for instance Tween-20, and the like. Usually, from one to five partsof dispersing agent per'onehundred parts of compound is a good operatingrange.

The quantity of inert solid or liquid carrier or diluent employed withrespect to the insecticidal compounds can be widely varied. It has,however, been found that, depending upon the carrier employed, fromabout 1% to and preferably from about 20% to 70% by weight of thecompounds, based on the weight of the inert car- EXAMPLE 6 Todemonstrate the effectiveness of the iminothiolane and the iminothianecompounds as pre-emergence herbicides, the following test is conducted:

Seeds of corn, radish and wheat are exposed to the test compound inaqueous media. They are held in intimate contact for three weeks afterwhich time observations are made on germination, deformation ofseedlings and kill. Employing the compounds of Example 1,2-iminothiolane hydrochloride and 2-iminothi-ane hydrochloride, allroots of the seedlings are killed at a concentration of 500 parts permillion.

EXAMPLE 7 To demonstrate the effectiveness of the compounds of thepresent invention with respect to insecticidal activity, the followingexample is presented:

A 65/35 acetone/water mixture at concentrations equal to 0.1% and 0.01%active ingredient comprising either2-dimethoXyphosphinothioyliminothiolane orZ-diethoxyphosphinothioyliminothiolane, is prepared. Sieva lima beanplants with their first pair of leaves three to four inches in size areinfested with approximately 100 to 200 adult mites per leaf about fivehours prior to testing. The infested leaves are dipped into the testsolutions for approximately three seconds, removed from said solutionand permitted to dry. The dried leaves are then placed on separatedishes in a constant temperature room at 80 F. and 60% relative humidityfor two days. After two days, each plant is examined and mortalitycounts are made. It is found that the above compounds, when applied at aconcentration of 0.01%, produce one-hundred percent kill of adult mites.

I claim:

1. An insecticidal and herbicidal composition consisting essentially ofan inert carrier and an effective amount of a compound of the formula:

wherein R R R R R R R and R are each a substituent selected from theclass consisting of hydrogen and lower alkyl; n is an integer from 0 to1; and Q is a substituent selected from the group consisting of H X andPZ(OR in which X is a halogen atom,

Z is a substituent selected from the group consisting of ReferencesCited UNITED STATES PATENTS 3,233,963 2/1966 Olin 712.5X 3,287,46611/1966 Klopping 71-25 X 3,293,265 12/1966 Heck 167 33 X 3,317,5625/1967 Addor 712.5X

JAMES O. THOMAS, 111., Primary Examiner.

1. AN INSECTICIDAL AND HERBICIDAL COMPOSITION CONSISTING ESSENTIALLY OFAN INERT CARRIER AND AN EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA: